Art of treating hydrocarbons



y 23,1944- c E. I-ZIEMMINGER 2,349,428

ART OF TREATING HYDROCARBONS Filed Dec. 50, 1959 CATALYS HOP COLQMN 28 t FZACT/GNAT/NG 1 am m cAsoL/ms -n 1 JI'GAM INLET Patented May 23, 1944 l UNITED -STATES PATENT OFFICE ART OF TREATING HYDROCARBON S Charles E. Hemminger, Westfield, N. J., assignoito Standard Oil Development Company, a corporation of Delaware Application December 30, 1939,. Serial No. 311,832. I

2 Claims. (oi. 196-49) The present invention relates to improvements in the art of treating hydrocarbon oils. More particularly, the present invention relates to improvements in the art of preparing from a relatively high boiling petroleum oil, a crackable 5; may e performedstock, 6' g" a gas It is believed that my invention will be best It is of course appreciated by me that understood by a concrete illustration setting merous schemes have been proposed heretofore forth 15 111 Fonnectlon Wlth drawing, j for obtaining a suitable feed stock for some manner In Whlch I may treat glVeIl Chargmg cracking operation but in so far as I am aware, 10'. Stock the sequence of steps which I employ and which A preducedhast ff l Prude hall/m5 an are hereinafter disclosed in the ensuing descripspeclfic gravlhi of 18 1S Introduced P the tion and claims have never been heretofore carg through hue I and then Pumped Into a F ried out. It is my belief that certain very defi- I 3 dlspose? m finown manner m Furnace Settmg nite advantages accrue from my process and 5 i col f fi g i i heated among others it may be mentioned that I am f E W1 s g ggq able to secure a cracking feed stock which is i ellpera g 0 1 relatively free of tar or gummy constituents, or 6 col 1 Se opera mg er ac pressure t of about pounds per square inch. The maar forming components, is of relatively low mo- 1 s 20 terial, as indicated, is withdrawn through line ecular weight and is otherwise of high quality.

4 and discharged into a fractionating column 5. Furthermore, I may obtain, according to my u The bottoms from this column are withdrawn process, a high yield of a crackable feed stock. a

through line 6 at a temperature of about 800 F. The prior investigators in this field have heatand then passed into the viscosity lowering reed a feed stock such as a reduced crude, frac- 1 5 actor 'I as shown. The bottoms from 5 may tionated the material to remove fractions boiling amount to about 35% by weight of material m t gas 011 range and above and .thereafter charged to column 5. These bottoms remain in subJectefi bottom from fractlonator to liquid phase reaction chamber 1 for sufficient vlscoslty breakmg operatlon t coktime to effect the desired reaction. For inmg operation In any eYenttheponqltwns were stance, they may remain in said drum for a Such m the pressure m the vlscoslty f period of between 1 and 2 minutes at a temperaor coking drum was greater than that in the ture of about 0 R to F and a pressure fractionation In my process I 0196mm under lower than that in column 5 and preferably P Such that the pressllre m h? a considerably lower as, for example, a pressure tlonatfor 15 than h m the vls'coslty of about 3 to 25 mm. of mercury, absolute presbreakmg Zone or m the cokmg drumsure, so that the viscosity of these bottoms fed Furthermore, I operate my process 11n P through line 6 is lowered from about 500 secditicns Slwh that I Obtam from F i onds at 210 F. to about 2000 seconds at 122 F. breaker or coker, a maximum quantity of gas oil. Furol. Viscosity The overhead product With or ove e combination of a 9 P e 40 drawn from reactor 1 at a temperature of about cosity lowering or coking operation witha cat- F. in line 3 is discharged t tar Sepa a yt ra p ss, m s it posslblc t rator 9 from which an overhead product is withtransfer a lower boiling gas oil to the catalytic drawn through line 10 and fed t fracti ncrackin operati t higher b i gas atlng column H, from which the overhead is t rning to the viscosity breaking cokin passed in condenser l2, and then discharged Where y Cracking and. polymeriz n 1t 15 from said condenser into receiving drum I4 from verted into a lower bo ling as Oil d a heavy which normally gaseous material is taken off a Which latter gas 011 is conducted to the overhead and a gasoline fraction is recovered Cr c g Ope d the heavy tar Withdrawn from the bottom of drum M. The bottoms from for use as a fuel oil, such as bunker C uel. 0 tar separator 9 are withdrawn through line 20 for some similar purpose. at a temperature of about 775 F. and these bot- To the accomplishment of the foregoing and toms may be employed as a fuel. As an altersimilar ends, I provide a suitable process and native procedure, the material in vessel 1 may combination of apparatus elements in which my remain for an extended period of time therein process may be performed, which process is fully 5 to produce a hard coke at the bottom of the said described hereinafter, reference being had to the accompanying drawing.

The drawing represents diagrammatically a combination of elements in which my invention vessel, this treatment requiring 2 to 5 minutes. In this operation, also, the vessel is operated under a pressure lower than that in column 5, e. g., a pressure of about 5 mm. of mercury absolute pressure. Somewhat higher pressures could be used, however, provided they are always lower than the pressure in column 5. In order to facilitate the operation in vessel 1, it is desirable to introduce superheated steam at a temperature of about 900 F. into line 6 through line 2|.

Referring now to fractionating column H, the bottoms thereof may be withdrawn through line 21 and returned to reactor I. A gas oil out may be withdrawn through line 28, at a temperature of about 725 F. A pressure of about 50 pounds per square inch gauge in line 28 may be developed by means of pump 29. This product, having a mid-boiling point of about 775 F., may then be discharged into heating coil 2 with the feed stock.

Referring again to column 5, the overhead material is withdrawn through line 3| at a temperature of about 800 F. This material has a mid-boiling point of about 700 F. In order to assist in the vaporization, steam is fed to the bottom of column 5 through line 22. This steam may be at a temperature of about 925 F. The material of line 3| is then discharged into injector 32 and meanwhile catalyst in the form of a powder, grains, granules, or the like is fed from a hopper 35 through a star conveyor 36 into line 31 and thence into injector 32 where it is dispersed in the material fed from line 3|. This catalyst may be an adsorbent material such as acid treated clay, silica-alumina gels and the like and preferably is at a temperature of about 1000 F. The amount of catalyst added to the oil may vary from /2 to 20 parts of catalyst per part of oil by weight. The dispersionrof catalyst in oil is discharged into line 40 and thence in superheating coil 4| disposed in furnace setting 42 where sufficient heat is added to elevate the temperature to about 950 F. The material leavthe furnace may be under a pressure of 15 pounds per square inch gauge. The superheated material is then discharged to a reaction zone (not shown) and subjected to known conditions of temperature, pressure, time of reaction, etc., to effect the desired conversion.

Numerous modifications of the present invention falling within the scope of the invention of the same will be obvious to those skilled in the art. For instance, reaction drum 1 may be a coil and furthermore, the viscosity-breaking or coking operation therein carried out may be accomplished in the presence of a powdered or granular material such as pumice or petroleum coke. Furthermore, the material in line 28 may be fed di rectly through line 28-a to line 3|, i. e. omitting return to coil 2 in furnace 3. This is an important modification of my invention, although not the preferred, for the reason that this material will not further burden the fractionation carried out in tower 5. The return of the material to line 3| thus enables reduction of the size of the tower 5 afiording therefore, a saving of equipment, installation and maintenance cost. Another advantage is that where hot regenerated catalyst is contained in receiver 35, the latter when mixed with the liquid product in line 28-a in injector 32 serves to supply a portion of the heat required to vaporize the product. Another general advantage of my process in all modifications is that the amount of gasoline produced in drum 1 is relatively small and this is important since the gasoline thus produced would be of low octane number.

What I claim is:

1. A process for treating crude residual oils to obtain vaporizable constituents suitable for further cracking treatment which comprises heating said oil to a temperature suificient to vaporize a portion of said oil, thereafter separating the vapors so formed from the unvaporized residue, reducing the pressure on the unvaporized residue so separated, maintaining said residue at said reduced pressure for a period between 1 and 2 minutes and at a temperature between 775 and 800 F. so as to materially viscosity break said residuum, thereafter separating the vapors formed during said viscosity breaking treatment, condensing a portion of said last-named vapors and combining the portion so condensed with said fresh oil prior to said first-named heating step.

2. A process for treating crude residual oils to obtainvaporizable constituents suitable for cata-.

lytic cracking which comprises heating said oil to a temperature sufiicient to vaporize a portion of said oil, thereafter separating the vapors so formed from the unvaporized residue, reducing the pressure on the unvaporized residue so separated, maintaining said residue at the reduced pressure for a period between 1 and 2 minutes and at a temperature between 750 and 800 F. so as to materially viscosity break said oil, thereafter separating the vapors formed during said viscosity breaking treatment from unvaporized residue, fractionating the vapors so separated to segregate a heavy condensate fraction, an intermediate condensate fraction and a light condensate fraction, combining said heavy condensate fraction with said first-named unvaporized residue prior to subjecting the same to said viscosity breaking treatment and combining said intermediate condensate fraction with said crude residual oil prior to said first-named heating step.

CHARLES E. HEMMINGER. 

